Journal of Sedimentary Research, 2011, v.

81, 248–265
Perspectives
DOI: 10.2110/jsr.2011.24

DOLOMITE IN PERMIAN PALEOSOLS OF THE BRAVO DOME CO2 FIELD, U.S.A.: PERMIAN REFLUX
FOLLOWED BY LATE RECRYSTALLIZATION AT ELEVATED TEMPERATURE

KATHERINE A. HARTIG,1 GERILYN S. SOREGHAN,2 ROBERT H. GOLDSTEIN,3 AND MICHAEL H. ENGEL2

1
Pioneer Natural Resources, 5205 North O’Connor Boulevard, Irving, Texas 75039, U.S.A.
e-mail: Katherine.Hartig@pxd.com
2
Conoco-Phillips School of Geology and Geophysics, University of Oklahoma, 100 East Boyd Street, Norman, Oklahoma 73019, U.S.A.
3
Department of Geology, University of Kansas, 1475 Jayhawk Boulevard, Lawrence, Kansas 66045, U.S.A.

ABSTRACT: Lower Permian Abo–Tubb subsurface strata of northeastern New Mexico, U.S.A. consist of 30 to 120 m of fluvial
and eolian deposits, containing numerous dolomitic paleosols. Dolomite in the Abo–Tubb interval occurs in discrete intervals,
interpreted as paleosols on the basis of recognizable horizonation and the presence of associated features such as ped structures
and rhizoliths. The dolomite commonly forms veins, rhizoliths, and discrete and coalesced nodules.
Petrographic analysis indicates four dolomite types present in paleosol horizons: microsparitic, pseudospherulitic, clear cement,
and cloudy (inclusion-rich) cement. Microsparitic dolomite constitutes most of (70%) the dolomite, and is stoichiometric, with
relatively low Sr and Na and elevated Fe and Mn. Pseudospherulitic dolomite forms 15% of the dolomite, and consists of
stoichiometric microspar and spar, with abundant fluid inclusions, low Sr, Na, and Fe, and elevated Mn. Clear dolomite cement
constitutes approximately 12% of the dolomite and is finely to coarsely crystalline with a relatively calcian composition, low Sr and
Na, and elevated Fe and Mn. The cloudy cement forms a minor (2%) phase of very coarsely crystalline rhombs with a calcian
composition, low Sr and Na values, and relatively high Fe and Mn. All dolomite types exhibit a mottled texture of moderate to
bright orange and red luminescence. Fluid-inclusion analysis was not possible on the most common (microsparitic) dolomite type,
but analyses on the coarser varieties reveal homogenization temperatures typically ranging from 70uC to 110uC and final melting
temperatures of ice ranging from 220uC to 234uC, suggesting fluids of high (25% by weight) salinity. Bulk-rock carbon and
oxygen isotopes of carbonate nodules and rhizoconcretions from four paleosol profiles most commonly exhibit mean d13C and d18O
values typically ranging between , 23 to 25.5% (VPDB) and 20.5 to 2.8% (VPDB), respectively. Sulfur isotopes were analyzed
for the overlying Cimarron Anhydrite interval and an anhydrite nodule near the base of the study interval. Both samples yielded
similar results, suggesting that brines that precipitated the Cimarron Anhydrite also influenced the study interval.
The dolomite in the Abo–Tubb interval is interpreted to have precipitated in multiple stages. Solid calcite microinclusions in
microsparitic and pseudospherulitic dolomite suggest that pedogenensis and groundwater penecontemporaneous with Early
Permian deposition led to precipitation of calcite rather than dolomite. Oxygen and sulfur isotope data indicate dolomitization,
from later reflux of brines associated with deposition of the overlying (Leonardian) Cimarron Anhydrite. Petrographic relations
and elevated temperatures and salinities recorded by the fluid inclusions in the coarse dolomite are consistent with
recrystallization of the earlier dolomite and precipitation of dolomite cement from warm saline fluids of a possible Tertiary
hydrothermal origin, just predating migration of mantle-derived gas into the Bravo Dome reservoir.
These findings offer insight into questions about the climate significance of dolomite in paleosols, origin of dolomite in
hydrothermally altered hydrocarbon reservoirs, and the long-term effect of CO2 sequestration in saline aquifers. The results
show that dolomitic nodules in paleosols may form as replacements of paleosol calcite long after the paleosol formed. Primary
pedogenic dolomite would undoubtedly have climatic and paleoenvironmental significance, but recognizing it as forming during
soil formation, as opposed to later dolomitization, is key in establishing that significance. Also, this study provides an example
of high-temperature recrystallization of low-temperature dolomite, a process hotly debated in discussions of dolomitized
hydrocarbon reservoirs with evidence for hydrothermal fluid flow. Finally, as a natural CO2 reservoir, the Bravo Dome system
shows that the long-term result of dissolution of CO2 into brines is predominantly carbonate mineral dissolution.

INTRODUCTION
Dolomite is more abundant in ancient carbonates than modern
carbonate environments, and laboratory synthesis of dolomite at surface
conditions is commonly unsuccessful (Hardie 1987) unless there is a
microbial input overcoming kinetic barriers (Vasconcelos et al. 1995; Van
Lith et al. 2003; Moreira et al. 2004; Roberts et al. 2004: Kenward et al.
2009). Nevertheless, precipitation of primary dolomite has been
documented in marine settings (sabkhas, lagoonal, and open), saline
evaporative lakes, and other low-temperature sedimentary environments
(McKenzie et al. 1980; Garces and Aguilar 1994; Wanas 2002). In these
settings, dolomite precipitates from seawater or lake water with high

Copyright E 2011, SEPM (Society for Sedimentary Geology) 1527-1404/11/081-248/$03.00

JSR PERSPECTIVES
Mg2+ concentrations. Additionally, primary, biogenically mediated
dolomite precipitation has been documented in anoxic, isolated lagoons
(Vasconcelos et al. 1995) and in evaporative lakes as a result of bacterial
sulfate reduction (Wright and Wacey 2005), with laboratory replication of
both processes (Vasconcelos et al. 1995; Wright 1999; Wright and Wacey
2005; Wacey et al. 2007).
The occurrence of primary dolomite in modern soils has been
documented only rarely, and typically in association with Mg-rich parent
material (e.g., basaltic host; Capo et al. 2000; Whipkey et al. 2002;
Whipkey and Hayob 2008) or induced by highly evaporative meteoric
and groundwater soil solutions (Kohut et al. 1995). In contrast, much of
the dolomite present in paleosols (ancient soils) has been attributed to
groundwater processes. Specifically, elevated evaporation rates coupled
with various groundwater processes have been documented to produce
Mg-rich groundwater capable of either precipitating dolomite or
dolomitizing a precursor calcite. Specific processes resulting in Mg-rich
groundwater include: (1) mixing of saline brines and fresh groundwater
(Searl 1988; El-Sayed et al.1991; Coloson and Cojan 1996); (2) calcrete
precipitation from nearby groundwater resulting in groundwater depleted
in Ca2+ and enriched in Mg2+ (Botha and Hughes 1992; Armenteros et al.
1995; Spötl and Wright 1992); (3) fluid movement through Mg-rich clays
(Pimentel 2002); and (4) introduction of brackish waters during post-
exposure marine transgressions in paleosols hosted on marine carbonate
(Wright 1999; Wright et al. 1997; Barnett et al. in press). As many
researchers have interpreted dolomite in paleosols as an indicator of
climate or atmospheric conditions (e.g., Wright and Tucker 1991; Spötl
and Wright 1992; Kessler et al. 2001; Alonso-Zarza 2003; Benito et al.
2005), it is necessary to determine if dolomite in paleosols formed during
pedogenesis, or as a result of later diagenetic alteration.
Diagenetic processes, both early and late, have been shown to
contribute to dolomite formation in paleosols. Specific mechanisms
associated with late diagenetic events might include: (1) movement of
warm hydrothermal fluids capable of precipitating and recrystallizing
dolomite (Gregg 1985; Gregg and Shelton 1990); and (2) burial processes
lacking such fluid movement (Gao and Land 1991; Montañez and Read
1992; Smith and Dorobek 1993).
This paper addresses the origin of dolomite in paleosols of lower
Permian fluvial and eolian deposits of northeastern New Mexico, U.S.A.
Much of the dolomite present in this system exhibits spatial and textural
attributes consistent with a pedogenic origin. Consideration of a variety
of petrographic and geochemical attributes together with stratigraphic
associations, however, suggest dolomitization of precursor calcite during
an early-stage seepage of evaporated (marine) brines, followed by later
diagenetic events of recrystallization and cementation attributed to
tectonic and hydrothermal processes. This work provides a new model of
dolomite in paleosols and thus broadens documentation and understand-
ing of the origin of dolomite in paleosols.
Through detailed petrographic and geochemical study, this work sheds
light on the origin of some hydrothermal dolomite. Hydrothermal
dolomitization is a popular model for explaining massively dolomitized
oil and gas reservoirs (e.g., Smith and Davies 2006; Davies and Smith
2006) and large volumes of ancient dolomite globally. Concerns about
sources of Mg and the nature of geochemical data have led to suggestions
of high-temperature recrystallization of low-temperature precursor
dolomite in such systems (Machel 2004). This study provides evidence
of recrystallization of low-temperature dolomite at elevated temperatures.
Finally, this study elucidates fluid flow and thermal history of one of
the most important CO2 reservoirs of North America, the Bravo Dome of
New Mexico. It adds important constraints on the tectonic and thermal
history, to allow the gas migration to be placed into the context of a more
extensive paragenesis, and thus tests hypotheses of long-term effects of
geologic CO2 sequestration in the subsurface. Both the geologic
sequestration of CO2, and CO2 as a resource for industrial purposes
249
and enhanced oil recovery continue as subjects of active research
(Broadhead 1990, 1998). The Bravo Dome field is long-term analog for
geologic CO2 sequestration. It results from geologically recent CO2
injection and thus provides ground truth for modeling efforts. Previous
research has shown that long-term analog studies are essential for
calibration of reactive transport models in such systems (e.g., Pearce et al.
1996; Baines and Worden 2004). In particular, this study adds essential
analog data on the reactivity of mineral phases in an arkosic aquifer used
for geologic CO2 sequestration.
GEOLOGIC SETTING
The Lower Permian Abo Formation and the overlying Yeso Formation
occur in the shallow subsurface of northeastern New Mexico adjacent to the
Bravo Dome paleohigh. The Bravo Dome uplift represents the southeast
plunging projection of the Sierra Grande uplift, which developed as a part
of the extensive late Paleozoic deformation related to the greater Ancestral
Rocky Mountains system (Fig. 1; Roberts et al. 1976; Ross and Ross 1986;
Broadhead and King 1988; Broadhead 1990). The Dalhart, Palo Duro, and
Tucumcari basins formed adjacent to Bravo Dome. The Bravo Dome
merges northwest with the Sierra Grande uplift and southeast with the
Amarillo uplift (Fig. 1). Paleogeographic reconstructions place the Bravo
Dome region in low, equatorial latitudes (, 0–10uS to N) during
Pennsylvanian and Early Permian time (Scotese 1999; Kessler et al. 2001).
The Abo–Tubb study interval consists of the Abo Formation and the
overlying Tubb Sandstone Member of the Yeso Formation, hereafter
referred to as the ‘‘Abo–Tubb’’ interval. In the Bravo Dome region, the
Abo–Tubb interval rests nonconformably on Precambrian basement and
is capped by the Cimarron Anhydrite Member of the Yeso Formation
(Fig. 2). The Abo–Tubb interval consists of orange and red to purple
siliciclastic strata of fluvial and eolian origin, with numerous interbedded
dolomitic paleosols (Kessler et al. 2001). Interval thicknesses throughout
the study area vary from 30 to 120 m, reflecting the subjacent
paleotopography of Bravo Dome (Fig. 3; Kessler et al. 2001). The age
of the Abo–Tubb interval is early Wolfcampian to early Leonardian (see
Kessler et al. 2001 for details).
The Abo–Tubb interval in the Bravo Dome forms the reservoir in a 10
TCF CO2 field (Broadhead 1990, 1993). The gas had a mantle source
(Staudacher 1987; Cassidy 2005; Gilfillan et al. 2008) and was likely
derived from degassing of basaltic magmas dating from 1 Ma to 8 ka,
with CO2 charging possibly continuing to the present (Broadhead 1998;
Baines and Worden 2004; Broadhead and Gillard 2004; Cassidy 2005).
Depositional and Pedogenic Facies of the Abo–Tubb Interval
This paper focuses specifically on the dolomite in paleosols of the Abo–
Tubb interval and builds on the detailed depositional and paleopedolo-
gical framework established by Kessler et al. (2001; outlined below).
Kessler et al. (2001) documented three primary depositional facies in the
study interval: (1) matrix-supported conglomerate deposits inferred to be
of fluvial origin and typically found near the base of the section; (2)
planar-bedded to cross-bedded sandstone deposits inferred to be of fluvial
origin, predominating in the middle of the interval; and (3) massive to
faintly laminated siltstone loess deposits predominant in the top of the
section. Thin (, 30 cm) intraclastic layers consisting of reworked mud
and pedogenic nodule rip-ups occur in fluvial strata.
On average, paleosols occur at 5 m intervals in the thickest (off-
structure) Abo–Tubb intervals and are more closely spaced in the thinnest
(on-structure) areas (Figs. 3, 4, 5). Paleosols range from 10 cm to 4 m
thick and are recognized by the presence of downwardly bifurcating
(inferred root) traces, ped structures, slickensides (on ped surfaces),
melanization (darkening), and carbonate nodules and rhizoconcretions.
Kessler et al. (2001) described three paleosol types: Vertic Dolosol, Vertic
250 K.A. HARTIG ET AL. JSR

FIG. 1.—Major late Paleozoic tectonic fea-

tures in the greater study area, southwestern
U.S.A. Patterned areas represent uplifts. Boxed
region around Bravo Dome denotes the study
area. Diagonal line represents the paleolatitude
line from Scotese (1999) (modified from Kessler
et al. 2001).

Protosol, and Dolic Protosol (terms slightly modified from the Mack et
al. 1993 classification scheme). The prefixes ‘‘dolo and dolic’’ are utilized
to highlight the presence of pedogenic carbonate textures in the paleosol,
which currently consist of dolomite. The prefix ‘‘vertic’’ is used to refer to
the presence of pedogenic slickensides. Vertic Dolosols typically
predominate in the lower one-third of the study interval, associated with
the fluvial conglomeratic facies, and they range in thicknesses from 20 cm
to 4 m. Vertic Protosols occur in the upper half of the study interval,
associated with the fluvial sandstone and eolian siltstone facies, and range
up to 1.2 m thick. Dolic Protosols typically occur in the upper half of the
study interval, range from 10 cm to 2 m thick, and are developed in
association with the eolian siltstone (loessitic) facies.

METHODS

FIG. 2.—Permian stratigraphy of the study region from Broadhead and King
(1988) and Kessler et al. (2001).
The study area contains a natural CO2 reservoir with abundant wells
and associated conventional cores. For this study, four wells were selected
from the thicker Abo–Tubb strata in the study area, since thicker
intervals are less likely to contain superimposed paleosols. The four
selected cores (Pittard #1, Nikkel #1, State F.T., and Libby #1; Figs. 4,
5) were logged, sampled, and photographed.
All macroscopic dolomite types were sampled from the selected cores at
various depths for petrographic analysis. Thirty polished thin sections
were stained with alizarin red-S and analyzed using both transmitted light
and cathodoluminescence (CL) to document microscopic attributes such
as crystal size, texture, and fabrics. Luminescence attributes were
obtained using a Technosyn cathodoluminescence microscope (with 9
to 11 kV and 80 to100 mA).
A subset of eight thin sections selected from Vertic Dolosol, Dolic
Protosol, and intraclastic zones at various depths of the Pittard #1 and
Libby #1 cores, and containing all recognizable dolomite forms, were
JSR PERSPECTIVES
selected for fluid-inclusion analysis (Fig. 5). Doubly polished thick (60 mm
thick) sections were impregnated with blue resin and mounted using cold-
curing epoxy. The fluid-inclusion sections were cut into small chips to
isolate targeted inclusions and placed in acetone to remove the epoxy. A
Linkam fluid-inclusion stage was utilized to measure homogenization
temperatures and low-temperature phase changes, using cycling methods
described in Goldstein and Reynolds (1994). Bulk salinities of fluid
inclusions were calculated from measured final melting temperatures
using published calibrations for the NaCl–CaCl2–H2O system (Oakes et
251
FIG. 3.—Fence diagram through studied wells
showing correlation of cored interval and general
depositional facies. See Figure 4 for well loca-
tions (modified from Kessler et al. 2001).
al. 1990) and the software of Bakker (2003). Because detailed ionic ratios
were not determined in this study, a model composition was assumed for
calculation of salinities (e.g., Goldstein and Reynolds 1994), using the
mean Na:Ca ratio analyzed from 82 oil-field brines (Carpenter et al. 1974;
Na:Ca wt. ratio of 2.1). Dissolved sulfate was not considered in
calculating salinity. Assumptions and calibrations for low-temperature
phase equilibria lead to minor errors in determination of fluid salinity.
Approximately 72 inclusions were analyzed, resulting in 72 homogeniza-
tion temperatures, 47 final melting temperatures of ice (Tm ice), and 4
FIG. 4.—Location map of wells in the Bravo
Dome study region in northeastern New Mexico,
with studied wells highlighted (modified from
Kessler et al. 2001).
252 K.A. HARTIG ET AL. JSR

FIG. 5.—Graphic columns of the four selected cores highlighting sample locations. Datum horizon is the base of the Cimarron Anhydrite.
JSR PERSPECTIVES
FIG. 6.—Photographs of macroscopic dolomite types. A) Dolomite rhizocretion and spar-filled rhizomolds in mottled red siltstone matrix (fine divisions are mm), B)
Dolomite calcrete nodules showing autoclastic fabrics typical of paleosols, in red siltstone matrix (fine divisions are mm), C) Dolomite, calcrete-filled fractures and
rhizoliths (scale in cm).
eutectics. All data were collected with careful constraint on their
petrographic association, using the fluid-inclusion assemblage (FIA)
approach of Goldstein and Reynolds (1994) and Goldstein (2003). The
FIA approach evaluates fluid-inclusion data on the basis of the most
finely discriminated events of fluid-inclusion entrapment that can be
identified petrographically.
Microprobe analysis was conducted on several thin sections selected from
the Vertic Dolosol, Dolic Protosol, and intraclastic zones and containing all
dolomite types. Thin sections were polished and carbon coated prior to
analysis. Samples were characterized at the University of Oklahoma
utilizing a Cameca SX50 electron probe microanalyzer, equipped with a
Kevex Delta-class energy-dispersive X-ray analyzer. Phase identification
and textural relations were examined by backscattered electron imaging
coupled with energy-dispersive X-ray analysis. Quantitative analysis was
performed by wavelength-dispersive spectrometry using beam conditions of
20 kV acceleration, 10 nA sample current, and a defocused 5 mm spot.
Natural crystalline solids were used as standard materials, counting times
were 45 s on peak for all elements, and matrix reduction used the PAP
method of Pouchou and Pichoir (1985). Calculated elemental thresholds are
as follows: 180 ppm (Ca), 245 ppm (Mg), 385 ppm (Sr), 133 ppm (Na),
245 ppm (Fe), 385 ppm (Mn), and 110 ppm (Si).
Four complete Vertic Dolosol profiles (Fig. 5) were logged at
centimeter-scale resolution and sampled for stable-isotope (C, O)
analyses. Core plugs (2 mm diameter) were drilled at 5 to 10 cm intervals,
targeting dolomite nodules and rhizoconcretions. Cores plugs were placed
in the hood and allowed to air-dry overnight. Samples were then
individually powdered using a mortar and pestle. These bulk samples are
meant to homogenize the material present rather than to use the stable
253
isotopes to discriminate the details of each diagenetic phase, because the
close spatial association of phases precluded the latter. Powdered samples
were digested in 100% phosphoric acid in sealed tubes under vacuum for
90 minutes at 100uC. The resultant CO2 gas was cryogenically isolated
and then analyzed with a Finnigan Delta E isotope-ratio mass
spectrometer. Values are reported in per mil relative to PDB carbonate.
The d18O values are corrected for fractionation at the 100uC run
conditions (Rosenbaum and Sheppard 1986).
Sulfur isotope analysis was conducted on two anhydrite samples. The
first sample was taken from the base of the overlying Cimarron Anhydrite
in the Nikkel #1 well. The second was sampled from an anhydrite nodule
located near the base of the study interval in the Libby #1 well. Samples
were powdered using a mortar and pestle and sent to Coastal Science
Laboratories for analysis.
DOLOMITE ATTRIBUTES
Macroscopic Attributes
Dolomite varies in concentration and morphology throughout all
paleosol types in the Abo–Tubb interval. Dolomite is most abundant in
the lower half of the study interval, and it typically occurs in nodules,
rhizoconcretions, and pores.
Dolomite nodules are spherical to tuberose, exhibit sharp to diffuse
boundaries, and are most common in Vertic Dolosols and Dolic
Protosols and are rare in Vertic Protosols. Nodules range in size from
, 1 cm to 10 cm in diameter, with the largest nodules occurring near the
base and the smaller discrete nodules and rhizoliths present in the upper
and middle parts of the study sections (Fig. 6). Nodules typically occur as
254 K.A. HARTIG ET AL. JSR
JSR PERSPECTIVES 255

TABLE 1.— Summary of geochemical data.

Mg % Na ppm
Dolomite Types Number of Samples Mean Range Std. Dev. (n) Mean Range Std. Dev.
Microsparitic 69 49 47.6 to 52.4 0.7 52 243 BDL to 988 130
Pseudospherulitic 10 48.5 4802 to 49.0 0.3 4 237 BDL to 368 92
Clear coarse cement 20 43.2 36.1 to 49.4 6 15 460 BDL to 965 316
Coarse cloudy 15 45.6 39.2 to 49.3 3.8 8 658 BDL to 2033 582
Mn ppm Fe ppm
Dolomite Types Number of Samples Mean Range Std. Dev. (n) Mean Range Std. Dev.
Microsparitic 69 1675 802 to 6504 691 55 1127 BDL to 6150 1006
Pseudospherultic 10 2733 2433 to 3382 265 2 * BDL to 6722 *
Clear coarse cement 20 2838 1618 to 4526 935 18 21824 BDL to 50498 19627
Coarse cloudy 15 5206 1964 to 8505 1883 7 41433 BDL to 70442 20761
* Indicates that statistics were not run due to the majority of the data values being below detection level (BDL).

vertically oriented cylindrical concretions and coalesced nodules (Gile et
al. 1966; Bachmann and Machette 1977; Machette 1985; Kessler et al.
2001). Vertically aligned nodules, which are , 1 cm in diameter, likely
represent examples of carbonate concretions around anastomosing root
traces (rhizoconcretions; Gile et al. 1966; Bachmann and Machette 1977;
Machette 1985; Kessler et al. 2001). Dolomite rhizoconcretions are
typically , 1 cm in width, and are abundant in the upper layers of
paleosol profiles (Bk horizons), with relative abundance diminishing with
depth.
Petrographic Attributes
Using petrographic analysis, the following four distinct dolomite types
were documented on the basis of crystal size, clarity, morphology,
presence of fluid inclusions, and cathodoluminescence attributes: (1)
microsparitic dolomite, (2) pseudospherulitic dolomite, (3) coarse cloudy
dolomite, and (4) dolomite cement.
Microsparitic Dolomite.—Microsparitic dolomite is the most common
type of dolomite. It occurs throughout the study interval in rhizoconcre-
tions and nodules and constitutes , 70% of all dolomite. Crystals range
in size from , 2.0 mm (cryptocrystalline) to 100 mm (medium crystalline)
and are typically equant, planar, subhedral rhombs in an idiotopic or
hypidiotopic mosaic. Crystals are tan to gray in transmitted light and
contain a moderate number of small (, 2 mm; Fig. 7A) fluid inclusions.
Cathodoluminescence analysis reveals moderate to bright orange and red
luminescence compared to coarser crystals, with areas of the brightest
luminescence present along crystal boundaries (Fig. 7B).
Microprobe analysis indicates that microsparitic dolomite is approx-
imately stoichiometric (49% Mg, 51% Ca: Table 1) with relatively low
amounts of Sr (BDL), Na (243 ppm), and Fe (1127 ppm). Manganese
(Mn; 1675 ppm) values are relatively high but lower than Mn values
measured from the other three types of dolomite.
There are two types of inclusions in the microsparitic dolomite: (1) two-
phase (liquid and gas) fluid inclusions, and (2) solid calcite inclusions. The
distribution of fluid inclusions and their orientation suggest they are
primary, either from initial precipitation of the dolomite or its
recrystallization. Fluid-inclusion analysis was not conducted on micro-
sparitic dolomite owing to the small inclusion size (, 2 mm).
Pseudospherulitic Dolomite.—Pseudospherulitic dolomite is most com-
mon in the lower half of the study interval (adjacent to the Precambrian
basement contact). Pseudospherulitic dolomite constitutes approximately
15% of the dolomite in the study interval, and typically it is found in
nodules and locally in rhizoconcretions. Crystals are polymodal, range
from 40 mm (finely crystalline) to 300 mm (coarsely crystalline), and
consist of nonplanar microspar and spar with anhedral to subhedral
dolomite rhombs in a xenotopic mosaic. This dolomite is typically tan to
clear in transmitted light, and it contains abundant fluid inclusions (2 mm
to 10 mm; Fig. 7C) that appear aligned in a radiating pattern originating
from the center of the crystal, thus producing a pseudospherulitic texture.
Cathodoluminescence reveals an overall mottled texture consisting of dull
to moderate orange and red luminescence. Areas with the brightest
luminescence are fluid-inclusion-rich zones, crystal rims, and cracks along
cleavage planes (Fig. 7D). Microprobe analysis indicates that pseudo-
spherulitic dolomite is relatively stoichiometric (48.5% Mg and 51.5% Ca;
Table 1) with low Sr (BDL), Na (mean 5 237) and Fe (BDL), and
elevated Mn (mean 5 2733; Table 1).
Two types of inclusions occur in the pseudospherulitic dolomite: (1)
two-phase (liquid and gas) fluid inclusions (Fig. 8); and (2) solid calcite
inclusions. The radiating pattern and textures of the fluid inclusion
cavities suggest a microbial origin similar to that of Rossi and Cañaveras
(1999). Their distribution and orientation indicate a primary origin.
Typically, these fluid inclusions appear in two dimensions with an area of
approximately 20% gas and 80% liquid. Fluid-inclusion analysis was
conducted on two fluid-inclusion assemblages (FIA), resulting in eight
homogenization temperatures (Th). The narrow range of Th values
indicates consistent temperatures in FIAs (Goldstein and Reynolds 1994)
from 77uC to 91uC with a mean value of 84.1uC (Table 2). Where FIAs
yield consistent Th, it is likely that fluid inclusions have not been altered
by thermal reequilibration (Goldstein and Reynolds 1994). Eight ice final
melting temperatures were determined and ranged from 220uC to 231uC,
with a mean of 226.3uC; one possible eutectic was measured at 243uC.
The low eutectic supports the assumed model composition of an NaCl–

FIG. 7.—Photomicrographs of dolomite types. A) Microsparitic dolomite in transmitted light. B) Microsparitic dolomite in CL. C) Pseudospherulitic dolomite in plane
light. D) Pseudospherulitic dolomite in CL. E) Dolomite cement in plane light; black line in pore represents a bubble in the epoxy. F) Dolomite cement in CL. G) Coarse
cloudy dolomite in plane light. H) Coarse cloudy dolomite in CL.
 256
K.A. HARTIG ET AL.

FIG. 8.—Photomicrographs of fluid inclusions in three dolomite types. A1) Microsparitic dolomite, A2) microsparitic dolomite, A3) microsparitic dolomite zoom, B1) pseudospherulitic dolomite, B2)
JSR

pseudospherulitic dolomite, B3) pseudospherulitic dolomite, C1) coarse cloudy dolomite with dissolved core, C2) coarse cloudy dolomite, C3) coarse cloudy dolomite.
JSR PERSPECTIVES 257

TABLE 2.— Summary of fluid-inclusion data.

Average Homogenization Homogenization Temperature

Dolomite Types Number of Samples Temperature (uC) (uC) Range Std. Dev.
Pseudospherulitic 8 84.1 77 to 91 5
Clear coarse cement 43 87.9 61 to 131 13.2
Coarse cloudy 21 88.8 81 to 111 7.2
Average Final Melting
Dolomite Types Number of Samples Temperature for ice (Tm ice) (uC) Range of (Tm ice) (uC) Std. Dev.
Pseudospherulitic 8 226.3 231 to 220 4.3
Clear coarse cement 28 225.7 233 to 221 3.9
Coarse cloudy 11 225.7 231 to 221 3.8
Dolomite Types Number of Samples Average weight % salts Range weight % salts Std. Dev.
Pseudospherulitic 8 25.1 21.7 to 26.3 1.9
Clear coarse cement 28 24.8 22.3 to 25.9 1.67
Coarse cloudy 11 24.8 22.3 to 26.3 1.33

CaCl2–H2O brine. Given the assumptions, the mean Tm ice yields a
salinity of 25.1 weight percent salt (Fig. 9; Table 2).
Clear Coarse Dolomite (Cement).—Clear coarse dolomite cement
occurs throughout the study interval and constitutes approximately
12% of the total dolomite present. Dolomite cement fills and lines pores
and cracks associated with rhizoconcretions. Two generations of cement
are distinguished on the basis of grain size, shape, crystal color, clarity,
and location in the pore. The first generation typically lines the inner
parts of pores and consists of finely crystalline (15 to 30 mm), unimodal
crystals exhibiting a drusy texture, consisting of equant, planar, subhedral
to anhedral dolomite, in a hypidiotopic mosaic. This generation is cloudy,
tan to gray in transmitted light, and contains only rare resolvable fluid
inclusions. Cathodoluminescence reveals moderate orange and red
luminescence with a mottled texture.
The second generation lines the outer rims ofpores and is medium (80 mm) to
coarsely crystalline (300 mm), unimodal crystals exhibiting a blocky texture
consisting of equant, planar, euhedral dolomite rhombs in a hypidiotopic
mosaic (Fig. 7E). Crystals are typically clear in transmitted light with
moderately abundant fluid inclusions (2 to 10 mm). In cathodoluminescence,
this generation exhibits an overall mottled texture with moderate to bright
luminescence and localized zones of bright luminescence along the outer edges
of some crystals (Fig. 7F). Microprobe analysis indicates a relatively calcic
composition(mean 5 43%,Mgandmean 5 57%Ca)withlowSr(BDL),Na
(mean 5 460 ppm), and elevated Fe (mean 5 21824 ppm), and Mn
(mean 5 2838) concentrations (Table 1).
Inclusions are interpreted as having a primary origin owing to their
localization in distinct growth zones. Inclusions may have been trapped
during the initial growth of the crystal or during later recrystallization.
They are typically two phase and 2 to 10 mm in size. They appear in two
dimensions and consist of 20% gas and 80% liquid (Fig. 8). Fluid-
inclusion analysis was conducted on thirteen separate FIAs and resulted
in forty-three homogenization temperatures ranging from 61uC to 131uC,
with a mean value of 87.9uC (Table 2). Five of the FIAs produced
consistent Th, yielding Th data ranging from 61uC to 13uC. Twenty-eight
ice final melting temperatures were determined and ranged from 221uC
to 233uC with a mean of 225.7uC; two eutectics were measured at 246uC
and 248uC. The low eutectics support an interpretation of an NaCl–
CaCl2–H2O composition for the brine (Crawford 1981). Mean salinity is
calculated to be 24.8 wt. % salts (Table 2; Fig. 9).
Coarse Cloudy Dolomite.—Coarse cloudy dolomite occurs in the lower
half of the study interval and represents approximately 2% of the total
dolomite. It is in nodules and is spatially associated with anhydrite
nodules. Crystals are polymodal, range in size from 0.1 mm to 2.5 mm
(very coarsely crystalline), and consist of equant, planar, euhedral to
subhedral dolomite rhombs present in a hypidiotopic mosaic. A small
percentage (, 10%) of these crystals have cores that have been dissolved
and remain open today. These dissolved cores may represent relatively
recent dissolution of the dolomite. Cloudy and clear zones alternate.
Cloudy zones contain abundant fluid inclusions (4 to 20 mm) whereas
clear zones contain only a few fluid inclusions (Fig. 7G). These crystals
exhibit moderate to bright, orange and red luminescence and an overall
mottled texture, with localized areas exhibiting concentric zonation.
Inclusion-rich zones display bright luminescence. Inclusion-poor zones
display moderate luminescence (Fig. 7H). Microprobe analysis indicates
that the coarse cloudy dolomite is relatively calcic (45.6% Mg and 54.4%
Ca; Table 1) with low Sr (BDL) and Na (658) and elevated Fe
(41433 ppm) and Mn (5206) concentrations (Table 1).
The coarse cloudy dolomite phase has inclusion-rich zones located in
specific growth zones (cloudy zones; Fig. 8C). These inclusions may have
been trapped during initial dolomite growth, or during later recrystalli-
zation. Inclusions are 2 to 10 mm, two-phase, and appear in two
dimensions with areas of approximately 25% gas phase and 75% liquid
phase. Fluid-inclusion analysis was conducted on five fluid-inclusion
assemblages and resulted in twenty-one homogenization temperatures
ranging from 81uC to 111uC with a mean value of 88.8uC (Table 2).
Eleven ice final melting temperatures were determined and ranged from
221uC to 231uC with a mean for 225.7uC; one eutectic was observed at
245uC. The low eutectic supports an interpretation of an NaCl–CaCl2–
H2O composition for the brine (Crawford 1981). Mean salinity is
calculated to be 24.8 wt. % salts (Table 2; Fig. 9).
Isotopic Attributes
Carbon and Oxygen Isotopes.—Four paleosol profiles from varying
stratigraphic depths were selected for carbon and oxygen isotope
analyses. The d13C values for the four paleosol profiles (Fig 10; Table 3)
exhibit relatively invariant trends, with average values around 23.84%
PDB (Profile A; Fig. 10, Profile A; Table 3) and 25.3% PDB (Profile B
and C; Fig. 10, Profiles B, C; Table 3). The d13C values exhibit marked
up-profile enrichment in profile D (from 25.5% to +0.49% PDB; Fig. 10,
Profile A; Table 3). For oxygen isotopes, profiles B and C exhibit
relatively invariant trends, and average values are between 20.3% and
20.6% (PDB; Fig. 10, Profile B, C: Table 3). Two profiles show more
variation, with d18O values in profile A exhibiting a slight up-profile
258 K.A. HARTIG ET AL. JSR

FIG. 9.—Fluid-inclusion data by fluid-inclusion assemblage (FIA). Samples for fluid-inclusion analysis were taken from the Libby and Pittard cores. Samples from the
Libby core consist of the coarse cloudy dolomite and the dolomite cement. Samples taken from the Pittard core consist of the pseudospherulitic dolomite. All dolomite
types exhibit similar homogenization temperatures, mostly ranging from 70uC to 110uC, with only a few outliers. The final melting temperatures for all three dolomite
types are similar and appear to cluster between temperatures of 220uC to 234uC.
JSR PERSPECTIVES
enrichment (d18O 5 0.0% to 2.0%), and d18O values in profile D
exhibiting marked up-profile depletion (d18O 5 +3.0% to 23.5% PDB;
Fig. 10, Profile A, D; Table 3).
Sulfur Isotopes.—In addition to the carbon and oxygen isotope data,
two samples were selected for sulfur isotope measurements. The first
sample from the Nikkel #1 core at the base of the Cimarron Anhydrite
(Fig. 5) yielded two d34S values of 10.3% and 10.4%. The second sample,
from an anhydrite nodule present near the base of the Abo–Tubb sections
in the Libby #1 core, included two d34S values of 9.6% and 9.7%.
DISCUSSION
As evinced by the macroscopic and microscopic attributes documented
both here and in Kessler et al. (2001), paleosols are clearly present in the
Abo–Tubb interval in northeastern New Mexico and all contain dolomite
as the sole carbonate phase, with the exception of calcite inclusions in the
dolomite. In addition to the pedogenic textures, some of the carbonate
present in the study interval exhibits attributes typical of groundwater
precipitation and additionally bears evidence for recrystallization (see
below). Although the carbonate in the study interval is now dolomite, it
may have precipitated either initially as dolomite or initially as calcite that
has subsequently been replaced by dolomite.
Early (Pedogenic) Carbonate Formation
Multiple macroscopic and petrographic features suggest that much of
the microsparitic dolomite currently present in the Abo–Tubb interval
formed initially as pedogenic carbonate (Fig. 11). Primary evidence for a
pedogenic origin of the carbonate in the Abo–Tubb interval is the
presence of typical pedogenic textures. For example, much of the micrite
occurs in the form of displacive nodules and vertically aligned tubules
(rhizoliths) concentrated in discrete (inferred Bk) horizons. Furthermore,
these horizons also exhibit ped structures (locally with slickensides), and
microsparitic dolomite occurs in the finest-grained (muddy) intervals.
These observations are in contrast to groundwater-associated carbonate,
which typically occurs in coarser-grained, more permeable intervals
(Pimental et al. 1996; Mack et al. 2000). Homogeneous microsparitic
dolomite predominates and commonly exhibits circumgranular cracking
and displacive textures consistent with pedogenic carbonate formation
(Pimental et al. 1996; Mack et al. 2000). Calcite inclusions suggest the
possibility that the dolomicrite formed initially as pedogenic calcite and
was later dolomitized. However, it is also possible that these inclusions
reflect dedolomitization of original pedogenic dolomite. Although it
remains possible that the dolomite formed as a primary pedogenic phase,
because other phases record evidence for later diagenetic dolomitization
events (discussed below), a simpler explanation is that these diagenetic
events similarly induced wholesale dolomitization of early pedogenic
calcite.
Carbon isotope values from the dolomite nodules and rhizoconcretions
in profile D could reflect a pedogenic trend, wherein d13C becomes
enriched up-profile, owing to the interaction of relatively enriched
atmospheric carbon with relatively depleted organic carbon (Cerling et al.
1989). However, the positive correlation between d13C and d18O in two of
the profiles suggests physical mixing of multiple diagenetic phases. The
overall negative d13C compositions could reflect preservation of the
original pedogenic signature despite probable later alteration. The d13C
values are consistent with values reported for paleosol carbonate
(Goldstein 1991; Mora and Driese 1999; Wright and Vanstone 1991).
Early Groundwater Carbonate Formation
Some authors have associated psuedospherulitic textures with low-
temperature groundwater processes (e.g., Pimental et al. 1996; Rossi and
259
Cañaveras 1999; Mack et al. 2000). Chafetz and Butler (1980) suggested
that pseudospherulitic textures form by the ‘‘neomorphism of Micro-
codium, or Microcodium-like globular bodies,’’ whereas Rossi and
Cañaveras (1999) linked pseudospherulitic textures to solution–precipi-
tation processes occurring at or near the water table, under predomi-
nantly oxidizing geochemical conditions, and possibly bacterially
mediated. Similar textures have been observed to form as siderite in
wetland soils (e.g., Stoops 1983; Ludvigson et al. 1998). We infer an initial
groundwater origin for the pseudospherulitic dolomite, but the rare
presence of solid calcite inclusions again suggests a possible early calcite
composition, and later dolomitization.
Taken together, these data indicate that groundwater processes that
occurred penecontemporaneous with deposition of the Abo–Tubb
interval in the early Permian resulted in precipitation of pseudospherulitic
calcite, which was later dolomitized, as further detailed below (Fig. 11).
The concentration of this dolomite phase in the lower half of the study
interval likely reflects groundwater fluid flow that was focused along the
Permian–Precambrian nonconformity surface.
Dolomitization (Seepage Reflux; Leonardian)
Given the kinetic and thermodynamic barriers to precipitating primary
pedogenic dolomite, and the mottled luminescence pattern and rare
presence of solid calcite inclusions in the microsparitic and pseudo-
spherulitic dolomite phases, we favor the interpretation that these phases
originated as calcite and were later dolomitized. Additional evidence from
the coarser phases, together with the stratigraphic setting, offer a
mechanism to achieve such dolomitization.
The Leonardian Cimarron Anhydrite directly overlying the Abo–Tubb
interval is likely a shallow evaporitic marine or mixed marine–nonmarine
evaporite unit (Hylton 1988; Hovorka et al. 1993). The conditions that led
to the deposition of the Cimmaron Anhydrite could have induced reflux
of Mg-rich (marine or mixed marine–nonmarine) brines through the
Abo–Tubb study interval. Oxygen and sulfur isotope data are consistent
with reflux of marine-influenced brines. Sulfur isotopes from both the
Cimarron Anhydrite and an anhydrite nodule near the base of the study
interval contain similar d34S values ranging from 9.6% to 10.4%,
suggesting that they were precipitated from a fluid of similar origin. These
d34S values are close to early Permian seawater values (, 12%; Claypool
et al. 1980; Strauss 1997). Oxygen isotopes also provide evidence for a
possible low-temperature, evaporated-fluid event of dolomitization.
Oxygen isotopes exchange readily during replacement, and so the current
d18O values exhibited in the paleosol profiles were likely altered during
initial dolomitization and later dolomite recrystallization (cf. Mora and
Driese 1999). The most positive d18O values present in the dolomite of the
Abo–Tubb interval likely approach values closer to initial dolomite
formation. These values cluster around 3%, and assuming about 3%
enrichment for dolomite relative to calcite (Land 1980; McKenzie et al.
1995) the values could reflect original values substantially enriched
relative to Permian seawater calcite values of 23.47 and 22.63% (Rao
and Green 1982; Rao 1988; Grossman 1994). With 3% dolomite
fractionation added, seawater dolomite would be expected around 20.5
to +0.5% The most positive oxygen values for dolomite are several per
mil more positive than those predicted from normal Permian seawater,
and are therefore consistent with dolomite precipitation from evaporated
Permian seawater or mixed marine–nonmarine water. These data are
consistent with the reflux interpretation. The more negative values likely
reflect diagenetic resetting at higher temperature.
Late Recrystallization (Cenozoic)
The coarse and cloudy dolomite cement and the pseudospherulitic
dolomite have mottled fabrics in CL, indicating recrystallization of an
260 K.A. HARTIG ET AL. JSR
JSR PERSPECTIVES
TABLE 3.— Summary of isotopic data.
Paleosol Number of
Profile Samples mean d13C d13C
A 15 23.84 22.42 to 24.35
B 13 25.24 25.38 to 25.06
C 14 25.32 25.47 to 25.19
D 11 24.29 25.37 to 0.49
earlier dolomite and a later dolomite-precipitating event (Fig. 11). Areas
with the brightest luminescence include inclusion-rich zones, mottles,
fracture fillings, and the outermost concentric growth zone, suggesting a
change in fluid conditions after initial crystal growth and fracturing that
led to cementation and recrystallization.
Cloudy and clear, coarse dolomite cement has elevated levels of Fe
and Mn relative to the microsparitic and pseudospherulitic dolomite.
The elevated Fe and Mn levels are consistent with hydrothermal fluids
(Schrijver et al. 1996) and deep basinal brines (Yoo et al. 2000), and
such elevated levels clearly record precipitation under reducing
conditions.
FIAs with consistent Th values (sensu Goldstein and Reynolds 1994)
yield homogenization temperatures between 70uC and 110uC, evidence
that high temperatures existed during dolomite cementation and
dolomite recrystallization. FIAs with inconsistent Th yielded values as
high as 131uC, indicating that the Abo–Tubb interval reached that
temperature after the dolomite existed. The fluid-inclusion eutectic
temperatures between 243uC and 248uC indicate abundant divalent
cations. Final melting temperatures for ice between 233uC and 220uC,
indicate approximately 24 weight percent salt. Thus, high-temperature
fluids that caused dolomite cementation and dolomite recrystallization
were highly saline and had chemistries other than simple NaCl. The
FIAs with consistent Th (70uC and 110uC) and those from inconsistent
Th (up to 131uC), are higher than the relatively low burial temperatures
estimated previously for the Abo–Tubb interval (, 50uC; Kessler et al.
2001). Upper Permian through Mesozoic overburden was likely , 300
to 1000 m (Broadhead 1990). Assuming a geothermal gradient of 25uC/
km, the maximum burial temperature of approximately 50uC is
inconsistent with fluid-inclusion Th values as high as 131uC. Thus,
the system was either conductively heated during a time of higher heat
flow or was subject to injection of warmer fluids into cooler rocks.
Systems with injection of aqueous fluids that are appreciably warmer
than ambient (5uC or greater; White 1957) are defined as hydrothermal,
and are worthy of consideration for recrystallizing and precipitating
dolomite.
Higher-Temperature Fluids
Dolomite formation induced by migration of hydrothermal fluids is
well documented (e.g., Gregg 1985; Schrijver et al. 1996; Durocher and
Al-Aasm 1997; White and Al-Aasm 1997; Reinhold 1998; Lonnee and Al-
Aasm 2000; Keller et al. 2000; Machel and Lonnee 2002). Dolomite
recrystallization and precipitation by hydrothermal fluids in the Abo–
Tubb interval requires a mechanism for upward fluid movement, which
could be related to deformation, volcanism in surrounding regions, or
both (Leach and Sangster 1993; Wojcik et al. 1997; Durocher and Al-
FIG. 10.—Paleosol profiles and associated isotopic values for paleosol profiles. All isotopic data are reported in per mil relative to VPDB. Profiles A, B, and C exhibit
relatively consistent d13C and d18O values throughout the profile. Conversely, Profile D exhibits significant changes in d13C and d18O values near the top of the
paleosol profile.
261
Std. Dev. mean d18O range d18O Std. Dev.
0.45 1.52 20.58 to 2.54 0.9
0.1 20.34 20.5 to .008 0.15
0.1 20.60 20.9 to 20.23 0.22
1.79 1.46 22.56 to 2.85 1.59
Aasm 1997; White and Al-Aasm 1997; Reinhold 1998; Lonnee and Al-
Aasm 2000; Keller et al. 2000; Cantrell et al. 2004; Smith and Davies
2006; Davies and Smith 2006).
Multiple tectonic and magmatic events have affected the region within
and around northeastern New Mexico since the deposition of the Abo–
Tubb interval. Specifically, regional tectonics associated with both the
Mesozoic Sevier Orogeny and Laramide Orogeny affected the greater
southern Rocky Mountain region, and more specifically the Raton Basin
region (Baltz 1965; Martinez 1989; Woodward 1987; Woodward et al.
1999). Dolomite-precipitating basinal fluid flow has been documented
extensively in relation to regional tectonic events; fluids derived from
adjacent deep basins coupled with faulting, uplift, permeable stratigraphic
units, and a basal unconformity could provide for the necessary pathways
for fluid migration (Gao et al. 1992a; Gao et al. 1992b; Gao et al. 1995;
Oliver 1992, 1996). In addition, late Cenozoic magmatism and extrusion
have been associated with the Spanish Peaks area (southern Colorado),
the Raton–Clayton volcanics, and the Rio Grande Rift (e.g., Manely
1984; Calvin 1987; Woodward 1987; Bove et al. 1995). Possible migration
of hydrothermal fluids into the study area in association with these events
is reasonable. The hydrothermal conditions recorded by fluid inclusions
in the dolomite, however, likely predated charging of CO2 into the Bravo
Dome reservoir. No clathrates were documented in the fluid inclusions,
and no CO2 fluid inclusions were observed, suggesting that CO2 had not
yet charged the reservoir during the late events of dolomite precipitation
and recrystallization. This observation is consistent with previous
interpretations that the CO2 charging was associated with recent basaltic
magmatism in the region, between 1 Ma and 0.8 ka (Broadhead 1998;
Baines and Worden 2004; Broadhead and Gillard 2004; Cassidy 2005).
Implications for CO2 Sequestration
Geologic sequestration of CO2 in subsurface saline aquifers has become
an active area of research as governments consider the effects of increased
atmospheric CO2 on climate change. Baines and Worden (2004) have
studied, as a natural analog for CO2 sequestration, several aquifer
systems in which the natural impact of CO2 addition could be evaluated.
The Bravo Dome is one such system where simple geochemical models
predicted that unstable silicates (e.g., calcic plagioclase, calcic zeolites,
clays) would dissolve and lead to carbonate precipitation after addition of
CO2 and its dissolution into the saline aquifer. Their findings were, on the
contrary, that the aluminosilicate reactions were likely too slow to
produce the predicted results, and that carbonate dissolution would be
the expected reaction. Our study confirms that late-stage dissolution of
minor dolomite phases are in fact the dominant mineralogical result of
CO2 injection, and that it is likely that the aluminosilicate reactions are
too slow to buffer the system.
262 K.A. HARTIG ET AL.
CONCLUSIONS
Lower Permian Abo–Tubb subsurface strata of northeastern New
Mexico consist of 30 to 120 m of fluvial and eolian deposits containing
numerous dolomitic paleosols. Macroscopic characteristics of much of
the dolomite appear pedogenic, but petrographic observations and fluid-
inclusion data coupled with microprobe data and isotopic data provide
evidence for dolomitization and recrystallization of the coarser phases in
particular. Although we cannot completely eliminate the possibility of a
primary pedogenic origin for the volumetrically predominant micro-
sparitic dolomite phase, the most reasonable explanation is that the
dolomite currently present in the Abo–Tubb interval was formed by a
series of later events. Implications of this are significant because dolomite
in paleosols has been interpreted, at times, as an indicator of climate or
atmospheric conditions during pedogenesis. If dolomite forms by later
replacement of paleosol calcite, then its presence is irrelevant for
interpreting paleoenvironment during soil formation. Hence, these results
reiterate the importance of careful diagenetic study of minerals in
paleosols, to disentangle primary from replaced phases.
After pedogenic and groundwater calcite formed during Early Permian
deposition (Wolfcampian–Leonardian), calcite was dolomitized in
association with low-temperature seepage reflux, during Early Permian
deposition of the overlying Cimarron Anhydrite (Leonardian). This Early
Permian dolomite was extensively recrystallized, and dolomite cement
precipitated from highly saline waters at temperatures well above those
that can be ascribed to normal burial heating. This alteration was mostly
likely caused by hydrothermal fluid flow associated with Cenozoic
JSR
FIG. 11.—Summary of paragenetic sequence
in the Abo–Tubb interval, outlining the various
events that have contributed to the carbonate
mineral paragenesis.
tectonism (Fig. 12). This example of high-temperature alteration of low-
temperature dolomite is useful in evaluating controversies about the
origin of dolomite in hydrocarbon reservoirs with hydrothermal
overprints.
Because the Bravo Dome system was initially charged with CO2 during
the last 1 Ma to 8 ka, the paragenesis is useful in testing hypotheses of
long-term mineral transformations associated with CO2 sequestration.
Given an aquifer of arkosic sandstone and minor carbonate phases, the
results show that the dominant initial mineral reaction after CO2 injection
will be dissolution of carbonate minerals. Aluminosilicate reactions
appear to be too slow to buffer the system and do not initially lead to
carbonate precipitation.
ACKNOWLEDGMENTS
This work represents research conducted for Hartig’s M.S. thesis under the
guidance of Dr. Gerilyn Soreghan, Dr. Michael Engel, Dr. Thomas Dewers,
and Dr. Robert Goldstein. This research was partially supported by the
donors of the Grants in Aid Foundation, administered by the American
Association of Petroleum Geologists. Acknowledgment is made to the donors
of the Petroleum Research Fund 35217-AC8, administered by the American
Chemical Society, for partial support of this research. Special thanks to Dr.
Mike Soreghan for technical assistance and guidance throughout this project
and to Dr. Kathleen Counter Benison for her guidance and mentorship. We
would also like to thank Eugene Rankey, Ronald Broadhead, and David
Barnes for their insightful comments and reviews regarding this paper.
Analytical and technical support at the University of Oklahoma was provided
by R. Maynard and M. Engel (stable isotopes) and G. Morgan (microprobe).
JSR PERSPECTIVES
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Received 18 April 2010; accepted 24 October 2010.